Compound and use thereof, organic electroluminescent device

Abstract

The present application provides a compound and its use, an organic electroluminescent device, the compound having a structure as shown in formula I, has better planarity and aromaticity, is easier to form an amorphous thin film, reduces the crystallinity of the molecule, and makes the spatial structure of the device more dense, thereby reducing the driving voltage and improving the luminous efficiency of the device; and has an arylamine structure of N, Ar 1 and Ar 3 are connected to adjacent positions of a benzene ring, respectively, and the LUMO level of the compound is shallowed, which further blocks the diffusion of excitons to the hole layer, and is more favorable for improving the performance of the device. The compound is applied to organic electroluminescent devices, particularly to electron blocking layer materials, which can reduce the operating voltage of the device, improve the luminous efficiency, and meet the needs for the continuous improvement of the photoelectric performance of OLED devices.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to a Chinese patent application filed on June 28, 2021 with the China Patent Office, application number 202110719948.2 and application title "Compound and its use for organic electroluminescent device," the entire contents of which are incorporated herein by reference.

[0002] Technical Field The present application belongs to the technical field of organic electroluminescent materials, in particular to compounds and their uses, organic electroluminescent devices. [Background technology]

[0003] In recent years, optoelectronic devices made of organic materials have become popular. The inherent flexibility of organic materials makes them well suited for fabrication on flexible substrates, allowing design and fabrication of aesthetically pleasing optoelectronic products on demand, which offers unparalleled advantages over inorganic materials. Examples of such organic optoelectronic devices include organic light-emitting diodes (OLEDs), organic field-effect transistors, organic solar cells, organic sensors, etc. The development of OLEDs has been particularly rapid, and they have achieved commercial success in the field of information display. OLEDs can provide three colors, red, green, and blue, with high saturation, and full-color display devices fabricated using them have the advantages of not requiring additional backlighting, being colorful, lightweight, thin, and flexible, etc.

[0004] The core of an OLED device is a thin film structure that contains multiple types of organic functional materials. Common organic functional materials include hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, light-emitting host materials, and light-emitting guests (dyes). When a current is applied, electrons and holes are injected and transferred to the light-emitting region, where they recombine to generate excitons, which then emit light.

[0005] At present, many kinds of organic materials have been developed, and by combining them with various novel device structures, it is possible to improve carrier mobility, control carrier balance, breakthrough in electroluminescence efficiency, and delay the decay of devices. For quantum mechanical reasons, general fluorescent emitters mainly emit light by singlet excitons generated when electrons and holes combine, and are still widely used in various OLED products at present. Some metal complexes (e.g., iridium complexes) can emit light by simultaneously using triplet excitons and singlet excitons, and are called phosphorescent emitters, and their energy conversion efficiency can be improved up to four times compared with traditional fluorescent emitters. Thermally excited delayed fluorescence (TADF) technology promotes the transfer of triplet excitons to singlet excitons, and can effectively utilize triplet excitons to achieve high luminous efficiency when metal complexes are not used. Thermally excited sensitized fluorescence (TASF) technology adopts materials with TADF properties to sensitize emitters through energy transfer, which can also achieve high luminous efficiency.

[0006] As OLED products enter the market, people have higher and higher requirements for the performance of these products. The currently used OLED materials and device structures cannot fully solve the problems in various aspects such as efficiency, lifespan, and cost of OLED products.

[0007] Therefore, there is an urgent need in this field to develop organic electroluminescent materials that can improve the luminous efficiency of devices and reduce their driving voltage. Summary of the Invention [Problem to be solved by the invention]

[0008] In view of the shortcomings of the prior art, the present application aims to provide a compound and its use, which is applicable to an organic electroluminescent device, and is particularly suitable for an electron blocking layer material and / or a hole transport layer material, and can improve the luminous efficiency of the device, reduce the driving voltage, and improve the overall performance of the device. [Means for solving the problem]

[0009] To achieve this objective, the present application adopts the following technical solutions:

[0010] A primary object of the present application is to provide compounds having the structure shown in Formula I. [ka] In formula I, X is O, S, CR 1 R 2 , N.R. 3 or SiR 4 R 5 is selected from.

[0011] In formula I, Ar 1 , Ar 2 are each independently any one selected from a substituted phenyl group, a substituted or unsubstituted C9-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group; and Ar 1 To [ka] If it contains, Z 1 is O, S, CR 11 R 12 or NR 13 * represents a bond to the group.

[0012] In formula I, Ar 3 is any one selected from a substituted or unsubstituted C6-C30 aryl group and a substituted or unsubstituted C3-C30 heteroaryl group.

[0013] R 1 , R 2 , R 3 , R 4 , R 5 , R 11 , R 12 , R 13are each independently any one selected from hydrogen, a substituted or unsubstituted C1-C20 linear or branched alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C12 alkenyl group, a substituted or unsubstituted C2-C12 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group; R 1 and R 2 , R 4 and R 5 , R 11 and R 12 are each independently unlinked or linked to the ring by a chemical bond.

[0014] R f1 , R f2 , R f3 are each independently any one selected from a halogen, a cyano group, a substituted or unsubstituted C1-C20 linear or branched alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C12 alkenyl group, a substituted or unsubstituted C2-C12 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group.

[0015] Ar 1 , Ar 2 , Ar 3 , R 1 , R 2 , R 3 , R 4 , R 5 , R 11 , R 12 , R 13 , R f1 , R f2 , R f3 The substituents in the above-mentioned substitutions are each independently at least one selected from a halogen, a C1-C10 straight or branched alkyl group, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, a C1-C10 alkoxy group, a C1-C10 alkylthio group, a C6-C30 arylamino group, a C3-C30 heteroarylamino group, a C6-C30 aryl group, or a C3-C30 heteroaryl group.

[0016] k1 and k2 each independently represent an integer of 0 to 3, for example, 0, 1, 2, or 3; k3 represents an integer of 0 to 4, for example, 0, 1, 2, 3, or 4.

[0017] The compound provided in the present application has a structure as shown in formula I, and the compound has better planarity and aromaticity, and is easier to form an amorphous thin film, and reduces the crystallinity of the molecule, making the spatial structure of the device more dense, thereby reducing the driving voltage and improving the luminous efficiency of the device; and the N, Ar of the arylamine structure are also preferable. 1 and Ar 3 are connected to adjacent positions of the benzene ring, respectively, and the LUMO level of the compound is made shallower, thereby further preventing the diffusion of excitons to the hole layer, which is advantageous for improving the performance of the element.

[0018] In this application, for the convenience of explanation, the possible actions of each group / characteristic are described separately, but this does not indicate that these groups / characteristics function in isolation. In fact, the reason for the good performance is essentially the optimal combination of the whole molecule, which is the result of the synergistic action of each group, not the effect of a single group.

[0019] In the present application, the halogen may be any of fluorine, chlorine, bromine or iodine. In the following, the same descriptions all have the same meaning.

[0020] In the present application, the "substituted or unsubstituted" group may be substituted with one substituent, or may be substituted with multiple substituents, and when there are multiple (at least two) substituents, they may be the same or different substituents. Hereinafter, the same descriptions all have the same meaning, and the selection range of the substituents is as shown above and will not be repeated here.

[0021] In this application, unless otherwise specified, the notation of a chemical element includes the concept of an isotope having the same chemical properties. For example, hydrogen (H) is1 H (proton hydrogen), 2 H (deuterium, D), 3 H (tritium, T) and carbon (C) 12 C. 13 Includes C.

[0022] In this application, unless otherwise specified, the heteroatoms in a heteroaryl group are selected from N, O, S, P, B, Si or Se.

[0023] In this application, the representation of a ring structure crossed with a "-" indicates that the linkage site is any available position in the ring structure.

[0024] In the present application, the expression Ca to Cb indicates that the number of carbon atoms in the group is a to b, and generally does not include the number of carbon atoms in the substituent, unless otherwise specified.

[0025] In this specification, the term "independently" means that when there are a plurality of subjects, they may be the same or different from each other.

[0026] In the present application, the C9-C30 aryl group may be any of C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, etc.

[0027] The C3-C30 may be any of C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, etc.

[0028] The C6-C30 may be any of C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, etc.

[0029] The C1-C20 may be any of C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, or the like.

[0030] The C3-C20 may be any of C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, etc.

[0031] The C2-C12 may be any of C3, C4, C5, C6, C7, C8, C9, C10, and C11.

[0032] Each of C1-C10 may be C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10.

[0033] The C3-C10 may be any of C3, C4, C5, C6, C7, C8, C9, and C10.

[0034] The C2-C10 may be any of C2, C3, C4, C5, C6, C7, C8, C9, and C10.

[0035] In the present application, the C6-C30 aryl group, preferably the C6-C20 aryl group, includes a monocyclic aryl group and a fused ring aryl group; the monocyclic aryl group refers to a group containing at least one phenyl group, and when the group contains at least two phenyl groups, the phenyl groups are connected to each other by a single bond, and examples thereof include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, etc. The fused ring aryl group refers to a group containing at least two aromatic rings, and two adjacent carbon atoms of the aromatic rings are fused to each other, and examples thereof include, but are not limited to, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, a fluorenyl group and derivatives thereof (9,9-dimethylfluorenyl group, 9,9-diethylfluorenyl group, 9,9-dipropylfluorenyl group, 9,9-dibutylfluorenyl group, 9,9-dipentylfluorenyl group, 9,9-dihexylfluorenyl group, 9,9-diphenylfluorenyl group, 9,9-dinaphthylfluorenyl group, a spirobifluorenyl group, a benzofluorene group, etc.), a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a perylenyl group, a chrysenyl group, or a tetracene group.

[0036] The C3-C30 heteroaryl group includes a monocyclic heteroaryl group and a fused ring heteroaryl group. The monocyclic heteroaryl group refers to a group containing at least one heteroaryl group in the molecule, and when the molecule contains one heteroaryl group and another group (e.g., an aryl group, a heteroaryl group, an alkyl group, etc.), the heteroaryl group and the other group are connected by a single bond, and examples thereof include, but are not limited to, a furyl group, a thienyl group, a pyrrolyl group, a pyridyl group, etc. The fused ring heteroaryl group refers to a group containing at least one aromatic heterocycle and one aromatic ring (aromatic heterocycle or aromatic ring) in the molecule, and two adjacent atoms share a fused group with each other. Examples include, but are not limited to, a benzofuranyl group, a benzothienyl group, an isobenzofuranyl group, an isobenzothiophenyl group, an indolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group and its derivatives (such as an N-phenylcarbazolyl group, an N-naphthylcarbazolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, an indolylcarbazolyl group, an azacarbazolyl group, etc.), an acridinyl group, a phenothiazinyl group, a phenoxazinyl group, and a hydroacridinyl group.

[0037] Specific examples of the arylene group described later in the present application include divalent groups obtained by removing one hydrogen atom from the above-mentioned aryl groups; specific examples of the heteroarylene group include divalent groups obtained by removing one hydrogen atom from the above-mentioned heteroaryl groups.

[0038] Examples of the C1-C20 linear or branched alkyl group include, but are not limited to, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, an n-octyl group, an n-heptyl group, an n-nonyl group, and an n-decyl group.

[0039] Examples of the C3-C20 cycloalkyl group include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group.

[0040] Preferably, X is CR 1 R 2 , N.R. 3 or SiR 4 R 5 and more preferably CR 1 R 2 It is.

[0041] Preferably, the R 1 , R 2 , R 3 , R 4 , R 5 are each independently any one selected from a substituted or unsubstituted C1-C6 linear or branched alkyl group, a substituted or unsubstituted C6-C18 aryl group, and a substituted or unsubstituted C3-C18 heteroaryl group; R 1 and R 2 is not linked or is linked to the ring by a chemical bond, R 4 and R 5 is unlinked or linked to the ring by a chemical bond.

[0042] Preferably, the R 1 , R 2 , R 3 , R 4 , R 5 are each independently a methyl or phenyl group.

[0043] Illustratively, X is CR 1 R 2 and R 1 and R 2 are linked by a chemical bond to form a fluorene ring structure.

[0044] Preferably, the Ar 1is any one selected from a substituted phenyl group, a substituted or unsubstituted C10-C20 aryl group, and a substituted or unsubstituted C12-C30 heteroaryl group; the heteroatom in the C12-C30 heteroaryl group is O, S, or N.

[0045] Preferably, the Ar 1 is one of the following substituted or unsubstituted groups: [ka] In the formula, * represents a bond of a group; R' is selected from halogen, a C1-C10 straight or branched alkyl group, a C3-C10 cycloalkyl group, a C1-C10 alkoxy group, a C1-C10 alkylthio group, a C6-C30 arylamino group, a C3-C30 heteroarylamino group, a C6-C30 aryl group, or a C3-C30 heteroaryl group.

[0046] Z 1 are O, S, and CR 11 R 12 or NR 13 is selected from.

[0047] R 11 , R 12 , R 13 are each independently any one selected from hydrogen, a substituted or unsubstituted C1-C20 linear or branched alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C12 alkenyl group, a substituted or unsubstituted C2-C12 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group.

[0048] R 11 and R 12 is unlinked or linked to the ring by a chemical bond.

[0049] n is an integer from 1 to 5, for example, 1, 2, 3, 4 or 5.

[0050] Preferably, the Ar 1 is any one selected from the following substituted or unsubstituted groups: [ka] In the formula, * represents a bond of the group.

[0051] Preferably, the Ar 2 is any one selected from a substituted phenyl group, a substituted or unsubstituted C10-C20 aryl group, and a substituted or unsubstituted C12-C30 heteroaryl group.

[0052] Preferably, the Ar 2 is any one selected from the following substituted or unsubstituted groups: [ka] In the formula, * represents a bond of a group; R″ is selected from halogen, C1-C10 linear or branched alkyl group, C3-C10 cycloalkyl group, C1-C10 alkoxy group, C1-C10 alkylthio group, C6-C30 arylamino group, C3-C30 heteroarylamino group, C6-C30 aryl group, or C3-C30 heteroaryl group; L is any one selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group; Z 2 are O, S, and CR 21 R 22 , N.R. 23 or SiR 24 R 25 Selected from; R 21 , R 22 , R 23 , R 24 , R 25are each independently any one selected from hydrogen, a substituted or unsubstituted C1-C20 linear or branched alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C12 alkenyl group, a substituted or unsubstituted C2-C12 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group; R 21 and R 22 is not linked or is linked to the ring by a chemical bond, R 24 and R 25 is unlinked or linked to the ring by a chemical bond; m is an integer from 1 to 5, for example, 1, 2, 3, 4 or 5.

[0053] Preferably, the L is any one selected from a single bond and the following substituted or unsubstituted groups. [ka] In the formula, * represents a bond of the group.

[0054] Preferably, the Ar 2 is any one selected from the following substituted or unsubstituted groups: [ka] In the formula, L is [ka] Any one of the following: * represents a bond of the group.

[0055] Preferably, the Ar 3 is any one selected from the following substituted or unsubstituted groups: [ka] In the formula, * represents a bond of the group.

[0056] Preferably, the R f1 , R f2 , R f3 are each independently any one selected from a halogen, a cyano group, a substituted or unsubstituted C1-C6 linear or branched alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C18 aryl group, and a substituted or unsubstituted C3-C18 heteroaryl group.

[0057] Preferably, k1, k2, and k3 are all 0.

[0058] When a substituent is present in the "substituted or unsubstituted" described above in the present application, the substituent is each independently at least one selected from a halogen, a C1-C10 straight or branched alkyl group, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, a C1-C10 alkoxy group, a C1-C10 alkylthio group, a C6-C30 arylamino group, a C3-C30 heteroarylamino group, a C6-C30 aryl group, or a C3-C30 heteroaryl group.

[0059] Preferably, the substituents are each independently at least one selected from a halogen, a C1-C10 straight or branched alkyl group, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, a C6-C30 aryl group, or a C3-C30 heteroaryl group.

[0060] Preferably, the compound has any one of the structures shown below in P1 to P590: [ka] [ka] [ka] [ka] [ka]

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[0061] In some embodiments of the present application, when the organic compound is selected from any one or a mixture of P2, P16, P20, P25, P28, P31, P38, P42, P44, P51, P129, P196, P221, P301, P341, P391, P441, P448, P461 or P501, it can be used as an electron blocking layer material and / or a hole transport layer material in an organic electroluminescent device, which can more effectively improve the luminous efficiency of the device and more effectively reduce the driving voltage.

[0062] A second object of the present application is to provide the use of the compounds according to the first object as applied to organic electroluminescent devices.

[0063] Preferably, the compounds are used as electron blocking and / or hole transporting materials in organic electroluminescent devices.

[0064] The compound of the present application can be applied to an organic electroluminescent device, as well as to a lighting device, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a sheet-type scanner, or an electronic paper.

[0065] A third object of the present application is to provide an organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic layer provided between the first electrode and the second electrode, wherein the organic layer contains at least one compound according to the first object.

[0066] Preferably, said organic layer comprises an electron blocking layer, said electron blocking layer comprising at least one compound according to the first object.

[0067] When the compound provided in the present application is applied to an organic electroluminescent device as an electron blocking layer material, it can significantly reduce the driving voltage of the device, improve the current efficiency, and improve the overall luminescent performance of the organic electroluminescent device.

[0068] Preferably, said organic layer comprises a hole transport layer, said hole transport layer comprising at least one compound according to the first object.

[0069] In a specific technical solution, the organic electroluminescent device (OLED) includes a first electrode, a second electrode, and an organic layer located between the first electrode and the second electrode, and the organic layer may be further divided into a plurality of regions, for example including a hole transport region, a light emitting layer, and an electron transport region.

[0070] In a specific embodiment, a substrate can be used below the first electrode or above the second electrode. The substrate is a glass or polymer material that has excellent mechanical strength, thermal stability, waterproofness, and transparency. The substrate for a display may have a thin film transistor (TFT).

[0071] The first electrode can be formed by sputtering or depositing a material that functions as the first electrode on the substrate. When the first electrode is an anode, it can be an oxide transparent conductive material such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), or any combination thereof. When the first electrode is a cathode, it can be a metal or alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof.

[0072] The organic layer can be formed on the electrode by methods such as vacuum thermal evaporation, spin coating, printing, etc. The compound used as the organic layer can be an organic small molecule, an organic macromolecule or polymer, and a combination thereof.

[0073] The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a single layer hole transport layer (HTL), including a single layer hole transport layer containing only one compound and a single layer hole transport layer containing multiple compounds. The hole transport region may be a multilayer structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL), where the HIL is located between the anode and the HTL, and the EBL is located between the HTL and the light emitting layer, and the HTL or EBL includes at least one compound having the structure of Formula I.

[0074] The material of the hole transport region may further be, but is not limited to, a phthalocyanine derivative such as CuPc, a conductive polymer or a conductive dopant-containing polymer such as polyphenylene vinylene, polyaniline / dodecylbenzenesulfonic acid (PANI / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (PANI / CSA), polyaniline / poly(4-styrenesulfonate) (PANI / PSS), an aromatic amine derivative including the compounds shown below as HT-1 to HT-51, or any combination thereof. [ka] [ka] [ka] [ka]

[0075] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of multiple compounds. For example, the hole injection layer may employ one or more of the compounds HT-1 to HT-51 above, or one or more of the compounds HI-1 to HI-3 below, or may employ one or more of the compounds HT-1 to HT-51 and dope one or more of the compounds HI-1 to HI-3 below. [ka]

[0076] The light-emitting layer includes a light-emitting dye (i.e., a dopant) capable of emitting different wavelength spectrums, and may further include a host material. The light-emitting layer may be a monochromatic light-emitting layer that emits a single color, such as red, green, or blue. A plurality of monochromatic light-emitting layers of different colors may be arranged in a plane according to a pixel pattern, or may be stacked to form a color light-emitting layer. When light-emitting layers of different colors are stacked, they may be spaced apart from each other or connected to each other. The light-emitting layer may be a single color light-emitting layer that can simultaneously emit different colors, such as red, green, and blue.

[0077] According to different technologies, the light-emitting layer material can adopt different materials such as fluorescent electroluminescent material, phosphorescent electroluminescent material, thermally activated delayed fluorescent light-emitting material, etc. In one OLED device, a single light-emitting technology can be adopted, or a combination of multiple different light-emitting technologies can be adopted. These different light-emitting materials classified into different technologies can emit light of the same color or different colors.

[0078] In one embodiment of the present application, the light-emitting layer adopts fluorescent electroluminescence technology, and the fluorescent host material of the light-emitting layer is selected from, but not limited to, one or a combination of BFH-1 to BFH-17 listed below. [ka]

[0079] In one embodiment of the present application, the light-emitting layer adopts fluorescent electroluminescence technology, and the fluorescent dopants of the light-emitting layer are selected from, but not limited to, one or more combinations of BFD-1 to BFD-24 listed below. [ka] [ka]

[0080] In one embodiment of the present application, the light-emitting layer employs phosphorescent electroluminescence technology, and the light-emitting layer host materials are selected from, but not limited to, one or a combination of PH-1 to PH-85. [ka] [ka] [ka] [ka]

[0081] In one embodiment of the present application, the light-emitting layer adopts phosphorescent electroluminescence technology, and the light-emitting layer phosphorescent dopant is selected from, but not limited to, one or a combination of GPD-1 to GPD-47 listed below. [ka] [ka]

[0082] In one embodiment of the present application, the light-emitting layer employs phosphorescent electroluminescence technology, and the light-emitting layer phosphorescent dopants are selected from, but not limited to, one or a combination of RPD-1 to RPD-28 listed below. [ka]

[0083] In one embodiment of the present application, the light-emitting layer adopts phosphorescent electroluminescence technology, and the phosphorescent dopant of the light-emitting layer is selected from, but not limited to, one or a combination of YPD-1 to YPD-11 listed below. [ka]

[0084] The OLED organic layer may further include an electron transport region between the light-emitting layer and the cathode. The electron transport region may be a single-layer electron transport layer (ETL), including a single-layer electron transport layer containing only one type of compound and a single-layer electron transport layer containing multiple types of compounds. The electron transport region may be a multi-layer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0085] In one embodiment of the present application, the electron transport layer material is selected from, but not limited to, one or a combination of the following: ET-1 to ET-73. [ka] [ka] [ka] [ka] In one embodiment of the present application, a hole blocking layer (HBL) is located between the electron transport layer and the light emitting layer. The hole blocking layer can adopt, but is not limited to, one or more of the compounds ET-1 to ET-73 above, or one or more of the compounds PH-1 to PH-46; it can adopt, but is not limited to, a mixture of one or more of the compounds ET-1 to ET-73 and one or more of the compounds PH-1 to PH-46.

[0086] The device may further include an electron injection layer located between the electron transport layer and the cathode, and the electron injection layer materials include, but are not limited to, one or a combination of LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, Mg, or Yb.

[0087] The thicknesses of the hole injection layer, hole transport layer, electron blocking layer, light emitting layer, hole blocking layer, electron transport layer and electron injection layer are not limited. In order to further improve the light emitting efficiency of the light emitting device and further reduce the driving voltage, the thickness of the hole injection layer is preferably 8 to 12 nm, the thickness of the hole transport layer is preferably 55 to 65 nm, the thickness of the electron blocking layer is preferably 30 to 40 nm, the thickness of the light emitting layer is preferably 35 to 45 nm, the thickness of the hole blocking layer is preferably 3 to 8 nm, the thickness of the electron transport layer is preferably 20 to 30 nm, and the thickness of the electron injection layer is preferably 0.8 to 1.2 nm. In particular, when the thickness of the hole injection layer is 10 nm, the thickness of the hole transport layer is 60 nm, the thickness of the electron blocking layer is 35 nm, the thickness of the light emitting layer is 40 nm, the thickness of the hole blocking layer is 5 nm, the thickness of the electron transport layer is 25 nm, and the thickness of the electron injection layer is 1 nm, the obtained electroluminescent device has better light emitting efficiency and lower driving voltage. Effect of the Invention

[0088] Compared with the prior art, the present application has the following beneficial effects:

[0089] The compound provided by the present application has a structure as shown in formula I, and the compound has better planarity and aromaticity, and is easier to form an amorphous thin film, and reduces the crystallinity of the molecule, making the spatial structure of the device more dense, thereby reducing the driving voltage and improving the luminous efficiency of the device; and the N, Ar of the arylamine structure are also preferable. 1 and Ar 3 are connected to adjacent positions of the benzene ring, respectively, and the LUMO level of the compound is shallowed, which further blocks the diffusion of excitons to the hole layer, and is more favorable for improving the performance of the device. The compound is applied to organic electroluminescent devices, particularly as an electron blocking layer material, which is more favorable for reducing the operating voltage of the device and improving the luminous efficiency, and meets the need for the continuous improvement of the photoelectric performance of OLED devices. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0090] The technical solution of the present application will be further described below by specific embodiments. For those skilled in the art, the above examples are only for understanding the present application, and should not be regarded as specific limitations of the present application.

[0091] In the present application, a representative synthetic route for a compound having the structure shown in Formula I is as follows. [ka] In the formula, Ar 1 , Ar 2 , Ar 3 , X, R f1 , R f2 , R f3, k1, k2, and k3 have the same meaning as in formula I, Pd(PPh3)4 represents tetrakistriphenylphosphinepalladium, Pd2(dba)3 represents tris(dibenzylacetone)dipalladium(0), Sphos represents 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, IPr.HCl represents 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride, NaOBu-t represents sodium-tert-butoxide, and (t-Bu)3P represents tri-tert-butylphosphine.

[0092] The preparation of the compound of formula I in the present application includes, but is not limited to, the above-mentioned methods, and the compound of formula I obtained by those skilled in the art through other synthesis methods also falls within the scope of protection of the present invention.

[0093] More specifically, the present application provides specific synthetic methods of the compounds as examples in the following synthetic examples, and the solvents and reagents used in the following synthetic examples can be purchased or customized from the chemical market, and those skilled in the art can also synthesize them by other known methods.

[0094] Mass spectrometry characteristic data in the following synthesis examples was measured using a ZAB-HS mass spectrometer manufactured by Micromass Ltd., UK.

[0095] Synthesis example 1: Compound P2 [ka]

[0096] In a 1000mL one-neck flask, 20.0g of M1, 20.7g of 2-biphenylboronic acid, 1.2g of tetrakistriphenylphosphine palladium Pd(PPh3)4, 28.9g of potassium carbonate, 300mL of 1,4-dioxane and 100mL of water were added, and the mixture was evacuated and replaced with nitrogen three times, and the reaction was heated to 100°C and reacted for 5h. The reaction was completed and stopped. The reaction was cooled to room temperature, the reaction liquid was separated, the organic phase was purified twice with a silica gel column, the organic phase was concentrated, methanol was added, and the mixture was refluxed and stirred for 1h, and then suction filtered to obtain pale yellow powder M1-1, which was then recrystallized with ethyl acetate to obtain 22.9g of pure product. M1-1: m / z theoretical value: 309; m / z actual value: 310.

[0097] In a 1000mL one-neck flask, 22.9g of M1-1, 13.5g of phenylboronic acid, 0.7g of tris(dibenzylacetone)dipalladium(0)Pd2(dba)3, 0.6g of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (Sphos), 31.4g of anhydrous potassium phosphate, 400mL of 1,4-dioxane and 40mL of water were added, and the mixture was evacuated and replaced with nitrogen three times, and the reaction was heated to 100°C and reacted for 5h. The reaction was completed and stopped. The reaction was cooled to room temperature, the reaction liquid was separated, the organic phase was purified twice with a silica gel column, the organic phase was concentrated, methanol was added, and the mixture was refluxed and stirred for 1h, and then suction filtered to obtain pale yellow powder M1-2, which was then recrystallized with ethyl acetate to obtain 16.9g of pure product. M1-2: m / z theoretical value: 351; m / z actual value: 352.

[0098] In a 1000mL one-neck flask, 16.9g of M1-2, 2ml of hydrazine hydrate, 0.5g of palladium carbon (Pd / C) and 300mL of ethanol were added, and the mixture was evacuated and replaced with nitrogen three times, and the reaction was heated to 90°C and reacted for 5h. The reaction was completed and stopped. The reaction solution was cooled to room temperature, and the organic phase was purified twice with a silica gel column, concentrated, methanol was added, and the mixture was refluxed and stirred for 1h. The mixture was filtered by suction to obtain a white powder M1-3, which was then recrystallized with ethyl acetate to obtain 14.5g of pure product. M1-3: m / z theoretical value: 321; m / z actual value: 322.

[0099] In a 1000mL one-neck flask, 14.5g of M1-3, 12.3g of 2-bromo-9,9-dimethylfluorene, 0.4g of Pd2(dba)3, 0.4g of 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (IPr.HCl), 13.0g of sodium-tert-butoxide NaOBu-t, and 300mL of toluene were added, evacuated and replaced with nitrogen three times, and the reaction was heated to 90°C and reacted for 5h. The reaction was completed and stopped. The reaction was cooled to room temperature, the reaction liquid was separated, the organic phase was purified twice with a silica gel column, the organic phase was concentrated, methanol was added, and the mixture was refluxed and stirred for 1h, and then suction filtered to obtain pale yellow powder M1-4, which was then recrystallized with ethyl acetate to obtain 17.1g of pure product. M1-4: m / z theoretical value: 513; m / z actual value: 514.

[0100] In a 1000mL one-neck flask, 17.1g of M1-4, 7.7g of 4-bromobiphenyl, 0.3g of Pd2(dba)3, 0.4mL of tri-tert-butylphosphine (t-Bu)3P, 9.6g of sodium-tert-butoxide, and 300mL of toluene were added, evacuated and replaced with nitrogen three times, and the reaction was heated to 110°C and reacted for 5h. The reaction was completed and stopped. The reaction solution was cooled to room temperature, the reaction liquid was separated, the organic phase was purified twice with a silica gel column, the organic phase was concentrated, methanol was added, and the mixture was refluxed and stirred for 1h, and then suction filtered to obtain pale yellow powder P2, which was then recrystallized three times with ethyl acetate to obtain 8.5g of pure product. Compound P2: m / z theoretical: 665; m / z actual: 666.

[0101] Synthesis examples 2 to 20, comparative compound CCP-3 The process routes of Synthesis Examples 2 to 20 are the same as Synthesis Example 1, with the difference being that the raw materials are different. The raw materials, target products and result characterization data are as shown in Table 1.

[0102] [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4]

[0103] Example 1 An organic electroluminescent device comprising, in order, an anode (ITO), a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode (Al).

[0104] The method for manufacturing the organic electroluminescent device is as follows: a glass plate coated with an ITO transparent conductive layer is ultrasonically treated in a commercial detergent, washed with deionized water, ultrasonically removed oil in a mixed solvent of acetone / ethanol, baked in a clean environment until moisture is completely removed, washed with ultraviolet light and ozone, and bombarded with a low-energy positive ion beam on the surface. The glass substrate with the anode is placed in a vacuum chamber, and the anode is heated to a temperature of <1×10 -5 The anode layer film was vacuumed to 10 Pa, and on the anode layer film, 10 nm of compound HT-4:HI-3 (97 / 3, w / w) mixture as a hole injection layer, 60 nm of compound HT-4 as a hole transport layer, 35 nm of compound P2 provided in the present application as an electron blocking layer, 40 nm of compound PH-61:PH-3:GPD-12 (100:100:20, w / w) ternary mixture as an emission layer, 5 nm of ET-23 as a hole blocking layer, 25 nm of compound ET-69:ET-57 (50 / 50, w / w) mixture as an electron transport layer, 1 nm of LiF as an electron injection layer, and 150 nm of metal aluminum as a cathode were vacuum thermally evaporated in sequence, and the total evaporation rate of all organic layers and LiF was controlled to 0.1 nm / s, and the evaporation rate of the metal electrode was controlled to 1 nm / s.

[0105] Examples 2 to 20, Comparative Examples 1 to 5 The organic electroluminescence device differs from Example 1 only in that the electron blocking layer material compound P2 is replaced with a compound in Table 2.

[0106] The structures of the electron blocking layer materials of Comparative Examples 1 to 5 are as follows. [ka]

[0107] The origin of the above-mentioned compound CCP-1 can be referred to the prior art CN109485577A, the origin of CCP-2 can be referred to the prior art KR1020180104911A, the preparation method of CCP-3 is as shown in Table 1, the origin of CCP-4 can be referred to the prior art CN107017348A, and the origin of CCP-5 can be referred to the prior art CN110903276A.

[0108] The organic electroluminescent devices according to the above Examples 1 to 20 and Comparative Examples 1 to 5 were subjected to the following performance tests: That is, the driving voltage and current efficiency of the organic electroluminescent devices were measured using a digital source meter and a luminance meter at the same luminance. Specifically, the voltage was increased at a rate of 0.1 V per second, and the luminance of the organic electroluminescent device was increased to 10,000 cd / m 2 The driving voltage, which is the voltage when the luminance was reached, was measured, and the current density at this time was also measured. The ratio of the luminance to the current density is the current efficiency. The test results are shown in Table 2.

[0109] [Table 2]

[0110] Referring to the data in Table 2, the compound provided by the present application is used in organic electroluminescent devices, which is advantageous in reducing the lighting voltage and improving the current efficiency. The device has a low driving voltage of 3.9 to 4.3 V and a current efficiency of 64.9 to 69.4 cd / A, and is a good-performance green photoelectron blocking layer material.

[0111] The difference between CCP-1 in Comparative Example 1 and compound P129 in Example 11 is the group Ar 2is a phenyl group, the planarity and aromaticity of CCP-1 are poor, which affects the crystallinity of the molecule and the compactness of the spatial structure, leading to a high driving voltage and low current efficiency of the device of Comparative Example 1. The difference between the compound CCP-2 of Comparative Example 2 and the compound P51 of Example 10 is that the group Ar 1 is a phenyl group, which increases the crystallinity of CCP-2 and reduces the density of the spatial structure, resulting in poor performance of the device of Comparative Example 2. In the molecular structure of CCP-3, there is a benzene ring between the arylamine N and the fluorene group (dibenzopentacene structure), which reduces the mobility and causes poor molecular stacking density, resulting in poor performance of the device of Comparative Example 3. In CCP-4, no substituent is connected to the ortho position of the arylamine N, which deepens the LUMO level of the molecule and reduces the light-emitting performance of the device. The electron blocking layer material of Comparative Example 5 is CCP-5, and the group Ar 1 is a silicon heteroaryl group, which leads to low mobility of CCP-5 and poor crystallinity of the molecule, which increases the driving voltage of the organic electroluminescent device and reduces the luminous efficiency.

[0112] The applicant has described the compounds and their uses, and the organic electroluminescent device of the present application through the above examples of the present application, but the present application is not limited to the above examples, that is, it does not mean that the present application cannot be carried out without relying on the above examples. Those skilled in the art should understand that any improvements to the present application, equivalent replacement of each raw material of the product of the present application and addition of auxiliary components, selection of specific methods, etc. are all within the protection scope and disclosure scope of the present application.

Claims

1. A compound characterized by having the structure shown in Formula I. 【Chemical Formula 1】 In the formula, X is O, S, CR １ R ２ 、NR ３ or SiR ４ R ５ selected from; Ar １ 、Ar ２ are each independently any one selected from a substituted phenyl group, a substituted or unsubstituted C9-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group, and Ar １ to 【Chemical Formula 2】 when included, Z １ is selected from O, S, CR １１ R １２ or NR １３ selected from; * represents the bond of the group; Ar ３ is any one selected from a substituted or unsubstituted C6-C30 aryl group and a substituted or unsubstituted C3-C30 heteroaryl group; R １ 、R ２ 、R ３ 、R ４ 、R ５ 、R １１ 、R １２ 、R １３ are each independently any one selected from hydrogen, a substituted or unsubstituted C1-C20 straight-chain or branched-chain alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C12 alkenyl group, a substituted or unsubstituted C2-C12 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group; R １ and R ２ 、R ４ and R ５ 、R １１ and R １２ are each independently either unconnected or connected to a ring by a chemical bond; R ｆ１ 、R ｆ２ 、R ｆ３ are each independently selected from any one of a halogen, a cyano group, a substituted or unsubstituted C1-C20 linear or branched alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C12 alkenyl group, a substituted or unsubstituted C2-C12 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group; Ar １ 、Ar ２ 、Ar ３ 、R １ 、R ２ 、R ３ 、R ４ 、R ５ 、R １１ 、R １２ 、R １３ 、R ｆ１ 、R ｆ２ 、R ｆ３ The substituents of the substitution in are each independently at least one selected from a halogen, a C1-C10 linear or branched alkyl group, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, a C1-C10 alkoxy group, a C1-C10 alkylthio group, a C6-C30 arylamino group, a C3-C30 heteroarylamino group, a C6-C30 aryl group, or a C3-C30 heteroaryl group; k １ 、k ２ are each independently an integer from 0 to 3; k ３ is an integer from 0 to 4.

2. Said X is CR １ R ２ 、NR ３ or SiR ４ R ５ and preferably CR １ R ２ ; Preferably, said R １ 、R ２ 、R ３ 、R ４ 、R ５is each independently selected from a substituted or unsubstituted C1-C6 linear or branched alkyl group, a substituted or unsubstituted C6-C18 aryl group, and a substituted or unsubstituted C3-C18 heteroaryl group; R １ and R ２ are unlinked or linked to the ring by a chemical bond, and R ４ and R ５ are unlinked or linked to the ring by a chemical bond; Preferably, the aforementioned R １ , R ２ , R ３ , R ４ , R ５ are each independently a methyl or phenyl group, and the compound according to claim 1 is characterized in that.

3. The aforementioned Ar １ is any one selected from a substituted phenyl group, a substituted or unsubstituted C10-C20 aryl group, and a substituted or unsubstituted C12-C30 heteroaryl group; the heteroatom in the C12-C30 heteroaryl group is O, S, or N; Preferably, the aforementioned Ar １ is any one of the following substituted or unsubstituted groups: 【Chemical Formula 3】 In the formula, * represents the bond of the group; R' is selected from halogen, a C1-C10 linear or branched alkyl group, a C3-C10 cycloalkyl group, a C1-C10 alkoxy group, a C1-C10 alkylthio group, a C6-C30 arylamino group, a C3-C30 heteroarylamino group, a C6-C30 aryl group, or a C3-C30 heteroaryl group; Z １ is O, S, CR １１ R １２ or NR １３ and; R １１ , R １２ , R １３is, independently of each other, any one selected from hydrogen, a substituted or unsubstituted C1-C20 linear or branched alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C12 alkenyl group, a substituted or unsubstituted C2-C12 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group; R １１ and R １２ are either unlinked or linked to the ring by a chemical bond; n is an integer from 1 to 5, the compound according to claim 1, characterized in that.

4. Said Ar １ is any one selected from the following substituted or unsubstituted groups, the compound according to claim 1 or 3, characterized in that. 【Chemical Formula 4】 In the formula, * represents the bond of the group.

5. Said Ar ２ is any one selected from a substituted phenyl group, a substituted or unsubstituted C10-C20 aryl group, and a substituted or unsubstituted C12-C30 heteroaryl group; Preferably, said Ar ２ is any one selected from the following substituted or unsubstituted groups, the compound according to claim 1, characterized in that. 【Chemical Formula 5】 In the formula, * represents the bond of the group; R″ is selected from halogen, a C1-C10 linear or branched alkyl group, a C3-C10 cycloalkyl group, a C1-C10 alkoxy group, a C1-C10 alkylthio group, a C6-C30 arylamino group, a C3-C30 heteroarylamino group, a C6-C30 aryl group, or a C3-C30 heteroaryl group; L is selected from any one of a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group; Z ２ is O, S, CR ２１ R ２２ , NR ２３ or SiR ２４ R ２５ selected from; R ２１ , R ２２ , R ２３ , R ２４ , R ２５ are each independently selected from hydrogen, a substituted or unsubstituted C1-C20 linear or branched alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C12 alkenyl group, a substituted or unsubstituted C2-C12 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group; R ２１ and R ２２ are not linked or linked to the ring by a chemical bond, R ２４ and R ２５ are not linked or linked to the ring by a chemical bond; m is an integer from 1 to 5.

6. The compound according to claim 5, wherein the L is any one selected from a single bond, a substituted or unsubstituted following group. 【Chemical Formula 6】 In the formula, * represents the bond of the group.

7. The Ar ２ is any one selected from a substituted or unsubstituted following group, and the compound according to any one of claims 1, 5 or 6 is characterized thereby. 【Chemical Formula 7】 In the formula, L is 【Chemical Formula 8】 selected from any one of; * represents the bond of the group.

8. The Ar ３ is any one of the following substituted or unsubstituted groups, and the compound according to claim 1 is characterized thereby. 【Chemical Formula 9】 In the formula, * represents the bonding site of the group.

9. Said R ｆ１ , R ｆ２ , R ｆ３ are each independently any one selected from a halogen, a cyano group, a substituted or unsubstituted C1-C6 linear or branched alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C18 aryl group, and a substituted or unsubstituted C3-C18 heteroaryl group; Preferably, said k １ , k ２ , k ３ are all 0, and the compound according to claim 1 is characterized in this.

10. The compound has any one of the structures shown in the following P1 to P590, and the compound according to claim 1 is characterized in this. 【Chemical Formula 10】 【Chemical Formula 11】 【Chemical Formula 12】 【Chemical Formula 13】 【Chemical Formula 14】 【Chemical Formula 15】 【Chemical Formula 16】 【Chemical Formula 17】 【Chemical Formula 18】 【Chemical Formula 19】 【Chemical Formula 20】 【Chemical Formula 21】 【Chemical Formula 22】 【Chemical Formula 23】 【Chemical Formula 24】 【Chemical Formula 25】 【Chemical Formula 26】 [Chemical Formula 27] [Chemical Formula 28] [Chemical Formula 29] [Chemical Formula 30] [Chemical Formula 31] [Chemical Formula 32] [Chemical Formula 33] [Chemical Formula 34] [Chemical Formula 35] [Chemical Formula 36] [Chemical Formula 37] [Chemical Formula 38] [Chemical Formula 39] [Chemical Formula 40] [Chemical Formula 41] [Chemical Formula 42] [Chemical Formula 43] [Chemical Formula 44] [Chemical Formula 45] [Chemical Formula 46] [Chemical Formula 47] [Chemical Formula 48] Claim 11 The compound is at least one selected from P2, P16, P20, P25, P28, P31, P38, P42, P44, P51, P129, P196, P221, P301, P341, P391, P441, P448, P461 or P501, and the compound according to claim 10 is characterized in that. Claim 12 Use of the compound according to any one of claims 1 to 3 in an organic electroluminescent device, a lighting device, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a sheet type scanner or an electronic paper; Preferably, the compound is used as an electron blocking material and / or a hole transporting material in an organic electroluminescent device.

13. An organic electroluminescent device, comprising a first electrode, a second electrode, and at least one organic layer provided between the first electrode and the second electrode, wherein the organic layer contains at least one compound according to any one of claims 1 to 3; Preferably, the organic layer includes an electron blocking layer, and the electron blocking layer contains at least one compound according to any one of claims 1 to 3; Preferably, the organic layer includes a hole transporting layer, and the hole transporting layer contains at least one compound according to any one of claims 1 to 3, an organic electroluminescent device characterized by this.

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